Alcohol synthesis process



.1.` K. MERTzwElLLER ALCOHOL SYNTHESIS PRocEss Fiied Nov. 1o, 195o March 9, 1954 dOPdZuOOuor MN m1 GJ JJEI. @QN 050.50@ e .Om .,111 .am No @e e W mnml 8 Mm db?(drmuum OU NI b m w @md 6m', IINM NN RMT wv. 1v @2525., ...Jrrm Om im ON- 6T L. 96 4N www a N Am k F40 a Al Gm J 0,1m, GNA @i d a@ ZOF J 2OQG U Facil Iwul Patented Mar. 9, 1954 ALCHOL SYNTHESIS PROCESS Joseph K. Mertzweiller, Baton Rouge, La., as-

signor to Standard Oil Development Company, a corporation of Delaware Application November 10, 1950, Serial No. 195,109

8 Claims. l

IThe present invention relates to an improved synthesis process for the production of alcohols by reacting organic compounds having oleiinic linkages with gas mixtures containing CO and Hz at high pressures and elevated temperatures in the presence of suitable catalysts. More particularly, the invention is concerned With an improved process for producing alcohols from olenic feed stocks which normally undergo the carbonylation reaction with difculty.

The synthesis of oxygenated organic compounds from olefinic compounds and mixtures of CO and I-Iz is now well known in the art. The olenic starting material is reacted in the liquid state with CO and H2 in the presence of a group VIII metal catalyst, usually cobalt. The primary reaction product consists essentially of organic carbonyl compounds, mainly aldehydes, having one more carbon atom more per molecule than the oleiinic feed material. The oxygenated product may then be hydrogenated in a second catalytic stage to convert the aldehydes to the corresponding alcohols.

Suggested as starting materials, have been practically all types of organic compounds having an olefinic double bond, including aliphaticl olens and diolens, cyclo-oleiins, aromatics with elenic side chains, oxygenated organic compounds with olenic double bonds, and the like. The metal may be'present as a solid or in the form of compound soluble in the olenic feed stock. Suitable reaction conditions include tempcratures of about 150-450 F., pressures of 10G-300 and higher atmospheres, H2 to CO ratios of about (L5-2:1, liquid feed rates of about 0.1 to 5.0 v./v./hr. and gas feed rates of 'about i000-, 45,000 standard cubic feet of gas mixture per barrel of liquid cleiin feed.

Similaior higher temperatures and pressures, and hydrogenation catalysts such as nickeLcoptungsten. oxides or sulfides of group VI and group VIII metals, etc. may be employed in' the second stage for hydrogenation of the carbonyl compounds to alcohols.

It has, however, been found that certain olens are considerably less adaptable to the alcohol synthesis process than others, and that, for a given olefin, one isomer may give an aldehyde and an alcohol yield of over 90%, another isomer of the same olefin may give a negligible yield of aldehyde and alcohol. These differences may be attributed to steric e'ects. Thus straight chain alpha olens are usually found to give the highest yield of reaction products, Whereas triand tetrasubstituted oleflns are highly resistant to reaction, and limit the conversion obtained in the synthesis reaction. This problem becomes particularly acute when the olefinic feed is not a pure compound but a mixture of isomers boiling Within a relatively narrow range and consisting of isomeric olens of the same molecular Weight. This is, of course, true in most commercial operations wherein it is not feasible to isolate pure compounds.

For instance, in the process of manufacturing octyl alcohols from heptene on a commercial scale, an abundant source of heptene is available from the controlled polymerization, in the presence of a phosphoric acid catalyst, of a mixture of butylenes and propylene, available in practically unlimited supply in petroleum reneres. The polymer is distilled and the heptene fraction is isolated. As would be expected, the product is a mixture of isomeric heptenes. It is convenient to classify olenic types in the following manner, depending upon the hydrogen loading of the olefinic carbons.

An analysis of a typical heptene polymer fraction boiling in the range of about 168 to 210 F., shows an olefin type distribution as follows:

It is thus seen that a preponderant fraction of the heptenes is present as tertiary olefins. Now

"though tertiary olefins of type III are quite reactive in the carbonylation reaction, others. particularly those represented by group V, react very slowly or not at all. For example, 2,3-di-methyl pentene-2 reacts with CO and Hz to form aldehydes at a substantially slower rate that it reacts With H2 alone to form the saturated paran. The presence, particularly of the type V type of olen in the feed to the primary carbonylation reactor puts a large burden on the final distillation section and cuts down materially the plant capacity, for either the olefins are recovered unchanged or as parafiins, both of which are undesired in a process where the primary purpose is to synthesize aldehydes and alcohols, giving as a nal result, low overall conversions of olefin.

It is, therefore, the principal purpose of the present invention to utilize more completely the olefin content of a feed to the alcohol synthesis process and to obtain high olen conversions.

It is also a purpose of the present invention to prepare a feed for the carbonylation reaction containing substantially less type V (tetrasubstituted) olens from polymers than has hitherto been possible, without resorting to expensive and diicult refractionation methods.

A further purpose of the present invention is to prepare a superior alcohol more suitable for employment as intermediate in the manufacture of plasticizers and detergents.

Other purposes and advantages of the invention will become apparent hereinafter.

The present invention overcomes these difficulties and affords various additional advantages. These advantages, the nature of the invention, and the manner in which it is carried out will be fully understood from the following description thereof read with reference to the accompanying drawing which shows a semi-diagrammatic view of apparatus adapted to carry out the invention.

In accordance with the present invention, the feed to the alcohol synthesis process is first reacted with formaldehyde at partial olefin conversion level, followed by treating the reaction product with CO and H2 to complete the olefin conversion. Under controlled conditions, as detailed below, the reaction between olens and formaldehyde may be controlled to be specic for tertiary olens. The reaction products are principally unsaturated alcohols and meta-dioxanes which, on hydrogenation, yield alcohols substantially isomeric with the alcohols obtained as end product from the alcohol synthesis reaction.

In one embodiment of the present invention, a feed to the synthesis process wherein the type V olefin content is minimized is prepared by treating an olen feed fraction containing vvarious tertiary olenic compounds with formaldehyde in the presence of a catalyst such as sulfuric acid or anhydrous stannic chloride, or at elevated temperatures without a catalyst, subjecting the product to distillation to remove olefins from oxygenated material, which is easily accomplished, and subjecting the olefins to the alcohol synthesis reaction with CO and H2, followed by hydrogenation of the aldehydes thus formed. The formaldehyde reaction products may be hydrogenated separately or, under certain conditions, it may be desirable to combine as the feed to the hydrogenation unit the aldehydes as well as the formaldehyde product.

In another embodiment of the invention, total product from the formaldehyde treatment is employed as feed to the alcohol synthesis reactor. With the combination of the two types of alcohol synthesis reactors, more complete and selective overall conversion of olefins is accomplished than could be achieved with either reaction carried out individually. Thus, olefin hydrogenation is minimized and maximum formaldehyde utilization is realized when excess olen is present, which is conveniently maintained without the expense of recycling in a partial conversion operation. Thus, depending upon the constitution of the olefins, a final product is obtained either mixed with or without, alcohols derived from the reaction of formaldehyde with tertiary olefins, which last-named alcohols are isomeric with the aldehyde-derived alcohols.

Having set forth the general nature, the invention will best be understood from the following more detailed description in which reference will be made to the accompanying drawing.

Referring now in detail to the figure, the system illustrated therein essentially comprises a formaldehyde pretreating unit 4, carbonylation reactor 24, decobalting vessel 42 and hydrogenator 50, whose function and cooperation will be explained below, using the treatment of a propylene-butylene polymer fraction boiling in the range of about 168 to 210 F. and consisting essentially of heptenes as an example. It is understood that the process is applicable in substantially analogous manner to the treatment of other mixtures or olefin streams, providing that such mixtures contain tertiary olefins.

In operation, a heptene fraction boiling in the range of about 168 to 210 F. and prepared by the polymerization of propylene and butylenes in the presence of a phosphoric acid catalyst is passed through line 2 into agitator 4. At the same time an amount of trioxymethylene, in molar proportions about equivalent to the tertiary olefins present in the feed, is added through line 6. The types of olefins present in the feed may readily be determined by infra-red or spectrographic analysis. Catalyst, such as stannic chloride, is admitted through line 8. About 0.05 to 0.5 mols catalyst per mol trioxymethylene is desirable. The resulting slurry is vigorously agitated, cooling being provided by coil l0. It is desirable that the temperature should not rise above about F. The reaction mixture, after a residence period of about 5 to 20 hours, is passed through line Il to processing equipment l2, wherein the material is washed, treated with soda to remove excess catalyst, and filtered, all in a manner known per se. The condensation product, comprising essentially, Cs unsaturated primary alcohols, and the unreacted material is passed via line I4 to still I6, wherein the product is fractionated. The unreacted heptenes are removed as overhead through line I3, and the bottoms product, containing the tertiary olefinformaldehyde condensate, is treated as described subsequently.

The overhead from still I6, composed essentially of primary and secondary olefins admixed with some tertiary olefins, but containing substantially less than the original olefin feed, is mixed in mixing chamber 20 with 1-3% of a catalyst promoting the reaction between olens and vH2 and CO introduced into mixing chamber 20 through line 2i. Hydrocarbon-soluble soaps such as cobalt stearato, oleate, or naphthenate and the like, may be employed. The solution' of catalyst in olefin is passed to the lower portion of primary reactor 24 through line 22.

Simultaneously, a gas mixture containing hydrogen and carbon monoxide in the approximate aumen.

ratio of 0.5-2 volumes of H2 per volume C0y is supplied through line 26. Reactor 24 is preferably operated at about 3000 p. s. i. g. and at a temperature of from about 250-400 F. The reactor may contain no packing, or may be packed with catalytically solid material, such as ceramic Raschig rings, pumice, and the like.

Liquid oxygenated reaction products, unreacted oleiins, and synthesis gases are Withdrawn from the top of the high pressure reactor 2d and are transferred through line 29 and cooler 28 to high pressure separator 30 where. unreacted gases are Withdrawn overhead through line 32., scrubbed in scrubber 34 of entrained metal carbonyl catalyst and may be recycled through line 30 to reactor 24 or used as required in other parts of the system.

Liquid products are withdrawn through line 38 from high pressure separator 30 and passed to catalyst removal zone t2 which may be a vessel packed with inert solid material of a nature similar to that in primary reactorV 24 or may also contain no packing. Hydrogen-comprising gases recovered from another stage of the process may,v

be supplied to catalyst removal zone 42 through line 44 and passed through zone 02 countercurrently to the liquid oxygenated product. Catalyst removal zone 42 is preferably maintained at a temperature of about 200 to 450 F., at which temperature the catalyst which enters Zone 42 predominantly in the form of metal carbonyl, such as cobalt carbonyl, dissolved in the liquid product is decomposed into metal and carbon monoxide. The metal may be deposited on the inert packing within zone 42 or on the Walls, Whilev the carbon monoxide may be purged by the hydrogen. A mixture of hydrogen and carbon monoxide may be Withdrawn through line d6 and sent to a methanizer or other suitable catalytic unit, wherein carbon monoxide may be converted into methane in any conventional manner, or the purge gas mixture may be used directly in hydrogenator 50 if a CO-insensitive hydrogenation catalyst such as the sulfactive catalysts, as sulfdes oi molybdenum, tungsten,

etc, is employed as hydrogenation catalyst.

Liquid oxygenated products now substantially free of carbonylation catalysts are withdrawn from catalyst removal zone $2 through line 48 and passed to the lower portion of hydrogenation reactor 50. Simultaneously hydrogen is supplied to reactor 50 through line 52 in proportions suiiicient to convert the organic carbonyl compounds in the oxygenated feed into the corresponding alcohols. l-Iydrogenator 50 may contain a mass of any conventional hydrogenation catalyst, for example, nickel, copper chromite, sulfactive hydrogenation catalysts such as tungsten sulde, nickel sulfide, molybdenum suliide, and the like. Depending upon thccatalyst, reactor 50 may be operated at pressures ranging from 3000 to 4500 p. s. i. g. and at temperatures of from vabout 300 to 500 F. and an H2 rate of from about 5000 to 20,000 normal cu. ft. per bbl. of feed. The catalyst may be in the form of xed or moving beds, or suspended in the liquid feed.

The products of the hydrogenation reaction and unreacted hydrogen may be withdrawn overhead through line 54 from reactor 50 then through cooler 56 into high pressure separator 58. Unreacted hydrogen may be Withdrawn overhead from separator 58 through line 60 and either vented or recycled to the hydrogenation reactor. The liquid products are withdrawn from separator 58 through line 6l to hydrocarbon still `$2, wherein are distilled overhead low-boiling products, mostly hydrocarbons boiling below the alcohol product desired. Thus when a C1 olefin fraction is theY feed to the process, generally the product boiling up to 340 F. is removed as a heads cut inV hydrocarbon still 62, and this material is withdrawn overhead through line El! and may be used as a gasoline blending agent if desired. The bottoms from this primary distillation are Withdrawn from hydrocarbon still B2 through line 66 and sent to alcohol still 08 where lthe product alcohols boiling in the desired range may be removed overhead by distillation at atmospheric pressures or under partial vacuum, depending upon the molecular weight of the alcohols.

Returning now to the bottoms product in still I6, the latter are Withdrawn through H for further processing. Though oleflns may be condensed With formaldehyde in a variety of Ways, this condensation in the presence of inorganic metal halide catalyst of the type of stannic chloride, zinc chloride, silicon tetrachloride, etc. yields preferentially unsaturated alcohols with one more carbon atom in the molecule than the olen from Which it derives.l These alcohols may, if desired, be isolated for utilization as solvents', etc. Preferably, however, they may be reduced to the corresponding saturated alcohols either separately, or they may, under certain circumstances, be hydrogenated together with the decobalted product from 42. Thus product withdrawn through line I1 may be passed to a separate hydrogenation oven 21 via line I9 or it may be passed, in Whole or in part, through line 23 for hydrogenation in hydrogenator 50, thus adding substantially to the overall yield of primary octyl alcohols.

The process of the invention may be subject to numerous modifications. Thus, as has been indicated above, under some circumstances, it may be desirable to pass the entire formaldehyde reaction product, after separation of the inorganic salts, said product including the unsaturated alcohols and the unreacted olelns, to the carbonylation reaction. inasmuch as the unsaturated alcohols formed in reactor l are also tertiary olenic alcohols. these olens do not undergo except to a very minor extent, the carbonyiation reaction with H2 and CO. Thus, total product from l2 may be passed via lines la and 25 to catalyst mixing unt 20 and thence passed to the carbonylation reactor 24, and a iinal yield of alcohol product is thus obtained considerably higher than if the original oleiin had not been pretreated with formaldehyde or its polymers. Thus, instead of trioxymethylene, gaseous formaldehyde, para-formaldehyde, or compounds which decompose to yield formaldehyde may be employed. It does not go to the heart of the present invention to disclose a process for reacting formaldehyde with lolefins; rather it is the purpose and object to disclose a novel combination including the formaldehyde processing step to increase alcohol yields and reactor capacities.

The invention may be further illustrated by the following specific examples, which clearly indicate the advantages obtainable from operating in accordance with the present invention.

392 grams (4.0. mois) of dry heptene fraction prepared by polymerizing propylene in the presence of butylene and a phosphoric acid catalyst,

7 and in addition, 360 grams (4.0 mols) of trioxymethylene were placed in-a 2-liter flask tted with a mechanical stirrer and a calcium chloride vamounted -to and had an API gravity of 46.9.

The following fractions were'segregatedby distillation:

.1 Fractionof UOP.Polymer.

tube. After stirring was commenced, 38 grams Wei ght percent (-25 111011.01 enhydreis Stamm monde Wes 5 1n 19s F. (350F. liquid temperaturen-- 61.85 added; cooling with wet ice was employed to keep Bottoms 38.15 the temperature as near as possible to 80 F., though a maximum of 120 E. was reachd-dl11` The olefin conversion in this case was 32%. mg a very short interval. Stirring was continued The onoonvertod olefin from this run was suh for 110111'5 end the product nered to remove lo jected to the carbonylation reaction in the presexeess trloxyrnethylene- The flltered prodoct ence of a cobalt catalyst, and equimolar proporwas` treated with 10% sodium caibonate solution tions of carbon monoxide and hydrogen at about until the aqueous layer was alkaline and no fur- 3000 pounds pressure and 350 F., and the prodrher preelmtete formed' The tm Carbonate Wes uct after hydrogenation was distilled and the oci'emoved by filtration, the layers separated and 15 1 h 1 d tyl a co o recovere the organic layer washed twice with distilled water and dried over anhydrous sodium sulfate. Example III Recovered was 370.7 grams (94.5%) material having an API gravity of 46.2. In this opera- The distillation bottoms from Examples I and tion 39 mol percent of the feed was converted. 20 II were composited and hydrogenated in an auto- The crude product was distilled on a mm. clave at 2800 p. s. i. g. hydrogen pressure at 350 Pod. column at atmospheric pressure and 5/1 F. for 12 hours over a nickel catalyst. The hyreflux ratio, the following fractions -being taken: drogenated product was light yellow in color and had a hydroxyl number of 140. Distillation on Weight percent 25 the 25 mm. Pod. column at 5/1 redux ratio led to III-195 F. (350 F- lllquld temperaturek 53-06 the isolation of the following fractions:

Bottoms 43.28 Water 3.66

Fraction Temrgeliaature, llyeightt, The unreacted hydrocarbon and olen feed me were subjected to olefin type analysis, with the 5 23 following results: iiss 27.03 :n.90 Type Feed Product 5 Bottoms Los l Example IV 55 61 The purpose of this example is to illustrate the 20 u I thermal (non-catalytic) condensation of a C1 10 olefin fraction isolated from a heptene polymer The above data indicate that there has been a Wlth formaldehydedistinct decrease in the tertiary olens from the In these experiments semmes of the olefm feed amount originally present in the feed. Especially, Were oonraered Wlth anhydrous formaldehyde 111 it is to ho noted that the type V olen Content' shaker antoclaves at temperatures of 350-400 namely, that type of olen wherein the oiennie F- 11% an mer# atmosphere; The products Which carbon atoms are attached to carbon atoms eonsred of e S111g1e 111111d poolse Were Washed rather than to hydrogen, has been decreased to W1t11 2% NaOH 11111211 the Weehmge Were Stror1g1y almost of its former talud Those tetro alkaline, washed with water and dried over ansubstituted olens are extremely resistant to reh ydrous Sod1111r1 sulfere- The products Were d15- ootion With carbon monoxide and hydrogen in 50 tilled on a 12 mch Vigreaux column to separate the presence of a cobalt carbonylation catalyst en unconverted fractenef C7 Oler and en 0X5" and their removal and conversion in accordance geneted freetlon 001151511111? pnmemly 0f unsetu" with the present invention increases to a subratTegealggle Illgarfs Wele sub-ect stantial e tent, the ca acit of the reactors. J

X p y ed to the oxo synthesis by treating with syn- Emmpze 1I thesis gas in the shaker autoclave in the presence of a metallic cobalt catalyst, followed by This run was made with 12 mols of the heptene hydrogenation over a nickel on kieselguhr catapolymer, 4 mols of trioxymethylene and 0.75 mol lyst. Oxo alcohols were recovered by COHVSII- of anhydrous stannic chloride. Conditions were co tional distillation. similar to those in Example I, stirring being con- Experimental data corresponding to such treattinued for 22 hours. The recovered product ing processes are given in the following table:

Run No 1 2 Feed (1) C1 (I) c1 Feed Weight, Gms 715 715 Formaldehyde, Gms 304. 5 302.0 Treating Conditions:

Temperature, F 350 400 Contact Time, Hrs 20 20 Pressure, p. s. i. g. Distillation of Product:

Unconverted Feed, Vol. Percent 77.0 72.0 Oxygenated Product 2l. 0 22. 0 Bottoms (Condensation Products)..- 1. 0 6.0

Run No 1 Oxonation and Hydrogenation of Unconverted Feed:

Hydro Hydro Catalyst Cat. Conc. Wt. Percent Temperature, F. Contact Time, Hrs

Ni-Kieselguhr... a.

Ni-Kieselguhr.

Distillation of Product:

Unconverted, Wt. Percent.. Intermediat AlcohoL cent Total Alcohol, Wt. Percent Many modifications of the invention may appear to those skilled in the art without departing from the spirit of the invention as described above. Thus, the condensation of formaldehyde with tertiary olens may be carried out as desired, with acid catalyst or it may be carried out at elevated temperatures without catalysts.

What is claimed is:

1. An improved process for producing primary alcohols from an olefinic feed stock containing substantial amounts of tetra substituted tertiary olefins as well as less highly substituted tertiary, secondary and primary olens which comprises reacting said feed stock with a compound selected from the class of formaldehyde and trioxyznethylene, maintaining reaction conditions including temperatures less than about 80 F, and a residence time of from 5 to 20 hours, selectively reacting tetra-substituted tertiary olens with said reagent and leaving substantially unchanged nontetra-substituted tertiary olens in said feed stock, whereby at least a substantial proportion of said tetra substituted oleflns is converted into oxygenated products comprising metadioxanes and unsaturated alcohols, further converting said oxygenated products into saturated primary alcohols, passing said olenic feed stock comprising tertiary, secondary and primary olefins but depleted in said tetra substituted oleiins to a carbonylation zone wherein olefins are reacted with carbon monoxide and hydrogen at elevated temperatures and pressures in the presence of a cobalt carbonylation catalyst and converted to aldehydes, passing a reaction product comprising aldehydes from said last-named zone to a hydrogenation zone and recovering high yields of primary alcohols.

2. The process of claim l wherein condensation products resulting from said first-named reaction are separated from unreacted olens.

3. The process of claim 2 wherein said condensation products are hydrogenated to produce primary alcohols.

4. The process of claim 3 wherein said condensation products are hydrogenated together with said aldehyde product in said hydrogenation zone.

5. The process of claim 1 wherein said feed stock is a heptene fraction.

6. An improved process for producing high yields of primary alcohols from an olenic feed stock containing substantial amounts of tetra substituted tertiary olens as well as less highly substituted tertiary, secondary and primary oleins which comprises reacting said feed stock with a compound selected from the group of formaldehyde and trioxymethylene at temperatures of less than about F. and for a period of from about 5 to 20 hours, selectively converting said tetra-substituted tertiary oleflns and leaving substantially unchanged non-tetra-substituted tertiary olens contained in said feed stock, whereby at least a substantial proportion of said tetra substituted oleiin is converted into oxygenated products comprising metadioxanes and unsaturated alcohols, passing said conversion product and unconverted olens to a carbonylation zone wherein said material is contacted at elevated temperatures and pressures with hydrogen and carbon monoxide in the presence of cobalt carbonyl whereby olens are converted into aldehydes containing one more carbon atom than said olens, passing said aldehydes and said firstnamed conversion products to a hydrogenation zone and hydrogenating both said aldehydes and said conversion products into primary alcohols.

'7. The process of claim 6 wherein said olefin feed comprises a heptene fraction containing about 20% of tetra alkyls substituted tertiary olen.

8. The process of claim 6 wherein said carbonylation conditions comprise pressures of about 2500 to 3500 pounds and temperatures of about 300375 F.

JOSEPH K. MERTZWEILLER.

References Cited in the le of this patent UNITED STATES PATENTS Name Date Mikeska et al. Jan. 12, 1943 OTHER REFERENCES Number 

1. AN IMPROVED PROCESS FOR PRODUCING PRIMARY ALCOHOLS FROM AN OLEFINIC FEED STOCK CONTAINING SUBSTANTIAL AMOUNTS OF TETRA SUBSTITUTED TERTIARY OLEFINS AS WELL AS LESS HIGHLY SUBSTITUTED TERTIARY, SECONDARY AND PRIMARY OLEFINS WHICH COMPRISES REACTING SAID FEED STOCK WITH A COMPOUND SELECTED FROM THE CLASS OF FORMALDEHYDE AND TRIOXYMETHYLENE, MAINTAINING REACTION CONDITIONS INCLUDING TEMPERATURES LESS THAN ABOUT 80* F. AND A RESIDENCE TIME OF FROM 5 TO 20 HOURS, SELECTIVELY REACTING TETRA-SUBSTITUTED TERTIARY OLEFINS WITH SAID REAGENT AND LEAVING SUBSTANTIALLY UNCHANGED NONTETRA-SUBSTITUTED TERTIARY OLEFINS IN SAID FEED STOCK WHEREBY AT LEAST A SUBSTANTIAL PROPORTION OF SAID TETRA SUBSTITUTED OLEFINS IS COVERTED INTO OXY- 